1 NON AQUEOUS SOLVENTS Mn(II)Mn(VI) Mn(VII )

2 I NTRODUCTION :- An inorganic nonaqueous solvent is a solvent other than water, that is not an organic compound. examples are liquid ammonia, liquid sulfur dioxide, sulfuryl chloride, phosphoryl chloride, antimony trichloride, bromine pentafluoride, hydrogen fluoride,other inorganic acids. These solvents are used in chemical research and industry for reactions.

3 Q UESTION Is non aqueous solvent ? A. NH3 B.Liquid SO2 C.HF D.All

4 C LASSIFICATION OF SOLVENTS Classification of solvents based on proton. Classification of solvents based on polar and non-polar solvents. Classification of solvents on Aqueous and non- aqueous solvents

5 TYPES OF NON AQUEOUS SOLVENTS: 1)PROTONIC AND NON PROTONIC SOLVENTS- THE SOLVENTS FROM WHICH PROTONS CAN BE DERIVED ARE CALLED PROTONIC SOLVENTS. eg. WATER,SULPHURIC ACID. THE SOLVENTS FROM WHICH PROTONS CAN NOT BE DERIVED ARE CALLED NON PROTONIC SOLVENTS.eg. LIQUID SULPHUR DIOXIDE,BENZENE,CHLOROFORM.

6 Protic or protonic solvents :- 2NH ₃ ⇌ NH ₄ + (ammonium) + NH ₂ − (amide) 3HF ⇌ H ₂ F+ + HF ² - (hydrogen difluoride) 2H ₂ SO ₄ ⇌ H ₃ SO ₄ + + HSO ₄ - (A)Acidic or protogenic solvents. H ₂ SO ₄,HCL,CH ₃ COOH,HCN. (B) Basic or protophilic solvents. NH ₃, N ₂ H ₄. Aprotic or non- protonic solvents:- C ₆ H ₆,CHCl ₃,CCl ₄,SO ₂. N ₂ O ₄ ⇌ NO+ (nitrosonium) + NO ₃ − (nitrate) 2SbCl ₂ ⇌ SbCl ₂ + (dichloroantimonium) + SbCl ₄ - (tetrachloroantimonate) POCl ₃ ⇌ POCl ₂ + + POCl ₄ -

7 2. ACIDIC,BASIC OR AMPHIPROTIC SOLVENTS:- THE SOLVENTS WHICH HAVE A TENDENCY TO DONATE PROTONS ARE ACIDIC IN NATURE AND ARE CALLED ACIDIC SOLVENTS.eg.acetic acid,HF. THE SOLVENTS WHICH HAVE STRONG TENDENCY TO ACCEPT PROTONS ARE BASIC IN NATURE AND ARE CALLED BASIC OR PROTOPHILIC SOLVENTS.eg.LIQUID NH ₃,C ₆ H ₅ N(PYRIDINE) etc. THE SOLVENTS WHICH NEITHER HAVE TENDENCY TO GAIN NOR TO LOSE PROTONS ARE CALLED AMPHIPROTIC OR AMPHOTERIC SOLVENTS.eg.H ₂ O,C ₂ H ₅ OH, etc.

8 3.IONISING AND NON IONISING SOLVENTS:- THE SOLVENTS WHICH ARE CAPABLE OF UNDERGOING SELF IONISATION(AUTO- IONISATION)ARE CALLED IONISING SOLVENTS.eg.H₂O,NH₃,SO₂, etc. THE SOLVENTS WHICH DO NOT IONISE AT ALL ARE CALLED NON-IONISING SOLVENTS.eg. BENZENE,HYDROCARBONS etc. -THESE ARE NON-POLAR IN NATURE.

9 4.CO-ORDINATING AND NON CO-ORDINATING SOLVENTS :- THE SOLVENTS WHICH ARE CAPABLE OF COORDINATING WITH THE METAL IONS OR ANIONS OF THE SOLUTE ARE CALLED CO-ORDINATING SOLVENTS. FOR eg.NH₃,SO₂,DMSO, DMF etc. ON THE OTHER HAND,THE SOLVENTS WHICH ARE NOT CAPABLE OF CO-ORDINATING WITH THE METAL IONS OF SOLUTE ARE CALLED NON CO-ORDINATING SOLVENTS. FOR eg.CCL₄, SATURATED HYDROCARBONS etc.

10 Q UESTION :- Which of the following are Amphiprotic solvents? 1 H ₂ SO ₄ 2 HCl 3 H ₂ O 4 CHCl ₃

11 Q UESTION :- Which of the following are example of protonic solvent? 1 HCN 2 CHCl ₃ 3 SO ₂ 4 CCl ₄

12 P HYSICAL PROPERTIES OF SOLVENTS :- Melting point and boiling point. Dielectric constant. Viscosity. o Dipole moment. o Heat of fusion & Heat of vaporisation. V(V) Cr(VI) Mn(VII)

13 LIQUID AMMONIA as non-aqueous solvent:- FREEZING POINT:- -77.7 ċ BOILING POINT:- -33.38 ċ DIELECTRIC CONSTANT:- 22.0 at -33.5 ċ LIQUID RANGE:- -77 to -33 ċ HEAT OF FUSION:- 0.018 kj mol¯¹ HEAT OF VAPORISATION:- 23.6 kj mol¯¹ SELF IONISABLE IN NATURE ACTS AS AN ASSOCIATED SOLVENT PHYSICAL PROPERTIES:-

14 WHY AMMONIA ACTS AS A BETTER SOLVENT THAN WATER:- POOR CONDUCTOR OF ELECTRICITY SPECIFIC HEAT OF AMMONIA IS GREATER THAN WATER LESS VISCOUS THAN WATER HIGH CRITICAL TEMPERATURE AND PRESSURE LESS ASSOCIATED THAN WATER(DUE TO LESSER HYDROGEN BONDING) DUE TO FORMATION OF STRONG REDUCING METAL –AMMONIA SOLUTIONS WITH AIKALI METALS.

15 C HEMICAL REACTION Acid base reaction. Precipitation reaction. Redox reaction. Solvation reaction.

16 TYPE OF REACTIONS IN NON AQUEOUS SOLVENTS:- 1) METATHETICAL OR PRECIPITATION REACTIONS:- THE REACTIONS IN WHICH PRECIPITATION OCCURS ON MIXING TWO SOLUTIONS ARE CALLED METATHETICAL OR PRECIPITATION REACTIONS. 2AgNO ₃ + BaCl ₂ → 2AgCl ↓ +Ba(NO ₃ ) ₂

17 2) SALT FORMATION :- THE REACTIONS BETWEEN APPROPRIATE ACIDIC AND BASIC SUBSTANCES TO FORM SALTS ARE CALLED SALT FORMATION REACTIONS.FOR eg,SODIUM UREIDE CAN NOT BE PREPARED BY THE ACTION OF UREA ON SODIUM HYDROXIDE IN WATER(BECAUSE STRONG BASE CAN NOT TAKE PROTON FROM UREA MOLECULE). Na ⁺ (NHCONH ₂ ) ⁻ + H ₂ O → Na ⁺ OH ⁻ + NH ₂ CONH ₂ ( SODIUM UREIDE) (UREA) HOWEVER,THIS CAN BE EASILY FORMED IN LIQ.NH ₃ BY REACTION OF UREA WITH SODAMIDE. NH ₂ CONH ₂ + Na ⁺ NH ₂⁻ → Na ⁺ (NHCONH ₂ ) ⁻ +NH ₃ (UREA) (SODAMIDE) (SODIUM UREIDE)

18 3)ACID BASE REACTIONS :- ACID BASE REACTION CAN BE EXPLAINED ON THE BASIS OF SOLVENT SYSTEM CONCEPT, AN ACID IS A SUBSTANCE THAT BY DIRECT DISSOCIATION OR REACTION WITH THE SOLVENT GIVES THE CATION CHACTERISTIC OF THE SOLVENT.SIMILARLY, A BASE IS A SUBSTANCE THAT GIVES THE ANION CHARACTERISTIC OF THE SOLVENT. FOR eg, IN LIQ. NH ₃ SOLVENT,NH ₄⁺ ION ACT AS ACID AND NH ₂⁻ IONS ACT AS BASE. THE NEUTRALISATION REACTION IS:- NH ₄ Cl + NaNH ₂ → NaCl + 2NH ₃ ACID BASE SALT SOLVENT

19 4) SOLVOLYTIC REACTIONS OR SOLVOLYSIS :- THE REACTIONS IN WHICH THE SOLVENT MOLECULES REACT WITH THE SOLUTE IN SUCH A WAY THAT THE SOLVENT MOLECULES SPLIT UP INTO TWO PARTS, ONE OR BOTH OF WHICH GET ATTACHED TO THE SOLUTE MOLECULE OR ION ARE CALLED SOLVOLYTIC REACTIONS. WATER AS SOLVENT:- 2H ₂ O↔ H ₃ O ⁺ + OH ⁻ (AUTO IONISATION ) SO ₂ Cl ₂ + 4 H ₂ O↔ SO ₂ (OH) ₂ + 2H ₃ O ⁺ +2Cl ⁻ F ⁻ +H ₂ O ↔ HF +OH ⁻ AMMONIA AS SOLVENT :- 2NH ₃ ↔ NH ₄⁺ + NH ₂⁻ SO ₂ Cl ₂ + 4 NH ₃ ↔ SO ₂ (NH ₂ ) ₂ + 2NH ₄⁺ + 2Cl ⁻ H ⁻ + NH ₃ ↔ NH ₂⁻ + H ₂

20 5) SOLVATION REACTION :- SOLVENT GET ATTACHED TO A SOLUTE SPECIES( CATION, ANION, OR MOLECULE) ARE CALLED SOLVATION REACTIONS.THE SPECIES FORMED IS CALLED SOLVATE. CuSO ₄ + 4NH ₃ → CuSO ₄.4NH ₃ (AMMONIATE) CuCl ₂ + 4 H ₂ O → [ Cu (H ₂ O) ₄ ]² ⁺ +2 Cl ⁻ (HYDRATE) BaSO ₄ + 3 H ₂ SO ₄ → BaSO ₄.3H ₂ SO ₄ (SOLVATE OF SULPHURIC ACID)

21 REACTIONS IN LIQUID AMMONIA 1)ACID BASE REACTIONS:- LIQUID AMMONIA IONISES AS:- 2NH ₃↔NH₄⁺ + NH ₂⁻ FOR eg. KNH ₂→ K⁺ +NH₂⁻ PROTOLYSIS REACTION:- Certain Compounds like UREA which are incapable of donating pprotons to water can readily donate proton to ammonia in liquid amonia. NH ₂ NH⁻ \ \ C = O + NH ₃ → C = O + NH₄⁺ ⁄ ⁄ NH₂ NH₂

22 2) ACID BASE NEUTRALISATION REACTION:- NEUTRALISATION OF AN ACID AND BASE IN LIQUID AMMONIA INVOLVES COMBINATION OF NH ₄⁺ ION(FROM ACID) AND NH₂⁻ ION(FROM BASE):- NH₄CI + KNH₂→ KCI +2NH₃ ACID BASE NH₄⁺ + NH₂⁻ → 2NH₃ AS AN ACID:- Zn(OH)₂ + KOH → K₂Zn(NH₂)₄ AS A BASE:- Zn(NH₂)₂ +2NH₄CI→ ZnCI₂ + 4NH₃

23 3) PRECIPITATION REACTIONS:- PRECIPITATION REACTIONS INVOLVE DOUBLE DECOMPOSITION BECAUSE OF THE DIFFERENCES IN SOLUBILITIES. KCl +AgNO ₃→ AgCl + KNO₃ WHITE PPT OF BaCl ₂ IS PRODUCED WHEN SILVER CHLORIDE AND LIQ. AMMONIA BROUGHT TOGETHER :- 2AgCl+ Ba(NO₃)₂↔ BaCl₂ (ppt)+ 2AgNO₃

24 4) AMMONOLYSIS REACTION:- THE SOLVOLYSIS REACTIONS IN LIQUID AMMONIA ARE CALLED AMMONOLYSIS OR AMMONOLYTIC REACTIONS. FOR eg.HYDROLYSIS OF SiCl ₄ OCCURS AS:- SiCl₄ +4H₂O ↔ Si(OH)₄ (Silicic acid) ORGANIC HALIDES UNDERGO SLOW AMMONOLYSIS REACTION TO FORM AMMINES :- RX + 2NH₃ → RNH₂ + NH₄X (Primary amines)

25 5) SOLUTIONS IN LIQUID AMMONIA:- THE MOST STRIKING PROPERTY OF LIQUID AMMMONIA IS ITS ABILITY TO DISSOLVE ALKALI METALS.THE RESULTING SOLUTIONS ARE BLUE AND GOOD ELECTRICAL CONDUCTORS. WHEN ALKALI METALS ARE DISSOLVED IN LIQUID AMMONIA THEY IONISE TO GIVE METAL IONS AND VALENCE ELECTRONS AS:- Na → Na⁺ + e⁻ Both alkali metal and electron become solvated by ammonia molecules.

26 Na ⁺ + xNH₃→ [ Na(NH₃)x]⁺ (ammoniated cation) e ⁻ + yNH₃ → [ e(NH₃)y]⁻ (amnoniated electron ) THE COMPLETE REACTION MAY BE WRITTEN AS:- Na → [ Na⁺ (NH₃)x]⁺ + [ e (NH₃)y]⁻ THE AMMONIATED ELECTRONS ARE RESPONSIBLE FOR BLUE COLOUR OF SOLUTION.

27 LIQUID SULPHUR DIOXIDE :- IT IS A NON –PROTONIC SOLVENT OR APROTIC SOLVENT BECAUSE IT DOES NOT CONTAIN ANY HYDROGEN ATOM. IT IS ALSO ONE OF THE IMPORTANT NON AQUEOUS SOLVENT AND WIDELY USED IN INDUSTRY. PHYSICAL PROPERTIES OF LIQUID SO ₂ :- FREEZING POINT :- -75.46 ċ BOILING POIN T :- -10.02 ċ DIELECTRIC CONSTANT:- 17.40

28 REACTIONS IN LIQUID SO ₂ :- 1) ACID BASE RACTION :- Liquid SO ₂ undergo auto ionisation as : 2SO₂ ↔ SO²⁺ + SO₃²⁻ Acid Base or Neutralisation reaction in liquid SO ₂ may be given as:- SOCl₂ + Cs₂SO₃ → 2CsCl + 2SO₂ (ACID) (BASE)

29 2) SOLVOLYTIC REACTIONS :- Solvolytic reactions in liquid SO ₂ are not so common as they are in other solvents such as NH₃. Certain covalent halides such as PCl₅,PBr₅, WCl₆ under go solvolysis in liquid SO₂ in sealed tubes. PCl₅ + SO₂ (liq) → POCl₃ + SOCl₂ PBr₅ + SO₂(liq) → POBr₃ + SOBr₂ WCl₆ +SO₂ (liq) → WOCl₄ + SOCl₂

30 3) PRECIPITATION REACTIONS :- Precipitation of several insoluble compounds in liq. Sulphur dioxide can be carried out by treating with soluble compound in SO ₂. SbCl₃ + 3LiI → SbI₃ ↓ + 3LiCl AlCl₃ + 3NaI → 3NaCl ↓ + AlI₃

31 4) REDOX REACTIONS :- Liq. Sulphur dioxide does show any marked reducing or oxidising property. It simply act as a medium for certain redox reactions. 6KI + 3SbCl ₅ → 2K₃[SbCl₆] + SbCl₃ + 3I₂

32 THANKS